This invention relates to alkoxysilyl functional silicone based materials, methods of making them and their uses. More particularly, the invention relates to thermodynamically stable materials comprising cross-linked siloxanes having alkoxysilyl functionality and a diluent, as well as to methods of making and the uses of such materials. The methods comprise cross-linking of reactants dispersed in a diluent.
Thermodynamically stable silicone based materials comprising cross-linked siloxanes dispersed in a diluent are known in the art. One such material, made by polymerization of certain organohydrogenpolysiloxanes along with organopolysiloxanes having aliphatic unsaturated groups while in the presence of certain low viscosity silicones, is disclosed in U.S. Pat. No. 4,987,169 to Kuwata et al. Another such material is disclosed in U.S. Pat. No. 5,760,116 to Kilgour et al. In this last instance, certain alkenyl stopped polyorganosiloxanes are hydrosilylated with xe2x89xa1SiH containing xe2x80x9cMQxe2x80x9d silicone resins in the presence of certain other silicones.
There are of course many variations possible in these materials and the synthesis of such materials. For example, the xe2x89xa1SiH groups and the aliphatic unsaturation may be on either or even both hydrosilylation reactants, as may other functionality. Sometimes, this allows for the synthesis of the same or a very similar type material using very different reactants in the same type of reaction. For example, what could be called a variant of Kilgour is seen in EP 1 057 476 by Fry, wherein the unsaturation appears in the resin and the xe2x89xa1SiH functionality appears in the other hydrosilylation reactant.
As with many other silicone based materials, it is has been found that inclusion of certain functional groups in the thermodynamically stable types discussed here can impart or enhance desirable properties. One example, where the polyether functionality is used, can be seen in U.S. Pat. No. 5,811,487 to Schulz et al. Here, the polyether functionality was introduced by hydrosilylation prior to cross-linking. It may also be of note that the cross linker may be purely hydrocarbon as was the case in this last mentioned material.
There is a continual need for new functionalized silicone based materials. New alkoxysilyl functional silicone based materials would be of great interest as they often have superior durability and/or enhance durability in formulations containing them.
Certain alkoxysilyl functional silicones and their formulations are well known in the art, notably as caulks, sealants and pressure sensitive adhesives. Such materials and methods for making them are exemplified by those disclosed in U.S. Pat. No. 5,470,923 to Krahnke et al. and U.S. Pat. No. 5,457,148 to Lucas. These prior art materials are not, however, thermodynamically stable (at least as defined herein below) and are usually much too effective in enhancing durability to be suitable for many applications in the personal care industry. In addition, use of these materials does not typically result in desirable aesthetics in many of the applications for which compositions of the present invention are designed.
The present invention provides thermodynamically stable, alkoxysilyl functional silicone based materials capable of suitably enhancing durability of personal care products while providing desirable aesthetics.
It is an object of the present invention to provide novel, thermodynamically stable, alkoxysilyl functional silicone based materials. In this regard, the invention relates to thermodynamically stable materials comprising:
(A) a cross-linked siloxane comprising:
alkoxysilyl functionality, xe2x80x94Xxe2x80x94SiR4n(OR5)3-n, and
cross-links, xe2x80x94E1xe2x80x94Yxe2x80x94E2xe2x80x94, with each end of such cross-links bonded to a silicon,
wherein,
X is a divalent group that is a hydrocarbon, a siloxane or some combination of these,
R4 and R5 are independently monovalent hydrocarbon groups,
E1 and E2 are independently xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94,
Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these, and
n is 0 to 2;
and
(B) a diluent.
It is a further object of this invention to provide methods of making thermodynamically stable, alkoxysilyl functional silicone based materials. Thus, the invention further relates to a method of making a thermodynamically stable material, the method comprising cross-linking, in the presence of a hydrosilylation catalyst,
(1) an xe2x89xa1SiH functional siloxane,
(2) an alpha, omega diene, diyne or ene-yne (as defined later herein),
with the provisos
that at least one of (1) and (2) has alkoxysilyl functionality, xe2x80x94Xxe2x80x94SiR4n(OR5)3-n,
where,
X is a divalent group that is a hydrocarbon, a siloxane or some combination of these,
R4 and R5 are independently monovalent hydrocarbon groups and
n is 0 to 2,
that (1) and (2) are dispersed in a diluent, and
that the weight ratio of (1)+(2)+ the product of the cross-linking of (1) and (2):diluent is 1:100 to 10:1.
The invention also relates to materials preparable, as well as those prepared by, the methods according to the present invention. In addition, the invention relates to personal care products containing the compositions of the present invention.
The compositions of the present invention include thermodynamically stable materials comprising:
(A) a cross-linked siloxane comprising:
alkoxysilyl functionality, xe2x80x94Xxe2x80x94SiR4n(OR5)3-n, and
cross-links, xe2x80x94E1xe2x80x94Yxe2x80x94E2xe2x80x94, with each end of such cross-links (meaning at E1 and E2 on the side opposite from Y as shown here) bonded to a silicon,
wherein,
X is a divalent group that is a hydrocarbon (especially one having 2 to 12 carbons), a siloxane or some combination of these,
R4 and R5 are independently monovalent hydrocarbon groups (especially those having 1 to 30 carbons),
E1 and E2 are independently xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94,
Y is a divalent group that is a hydrocarbon (especially one having 1 to 30 carbons), a siloxane or some combination of these and
is 0 to 2;
and
(B) a diluent.
(These compositions will be denoted hereinafter for convenience as those xe2x80x9cexplicitly definedxe2x80x9d.)
In the context of this disclosure and the claims that follow, thermodynamically stable refers to a material comprising a cross-linked polymer and a diluent that is homogeneous immediately after shearing and remains as such for at least 72 hours after being sheared, where homogeneous refers to something with a constant bulk viscosity (the type measured in units of cP, mPa s or equivalent units such as in a Brookfield device and sometimes referred to as absolute viscosity as opposed to kinematic viscosity) throughout a given sample within +/xe2x88x9210 percent.
One method for determining such thermodynamic stability is the Dow Corning Corporation Thermodynamic Stability test (hereinafter, the xe2x80x9cDCCTS testxe2x80x9d), wherein a sample of material is first sheared then visually inspected for homogeneity. If the sheared material is found to be visually homogenous, then viscosity is measured using a statistically significant number of random samples of the sheared material taken immediately after the visual inspection and again 72 hours later. The material is considered thermodynamically stable if all viscosity measurements (for accuracy""s sake, these are taken as, respectively, the mean of several measurements at the same point) from the initial sampling and the sampling 72 hours later are within +/xe2x88x9210 percent of their respective means.
Alkoxysilyl functionality is normally associated with the backbone portion of the cross-linked siloxane, but it may occur in the cross links or even in both the backbone and cross links at the same time and this disclosure and claims that follow should be interpreted to include these variations whenever possible, unless otherwise indicated. Of course in polymers made from similarly sized backbone components and cross linkers, it can be a little difficult to determine which is which in the final polymer, but this distinction usually makes no difference except for convenience in discussion.
It is possible a particular polymer molecule may have several different types of backbone elements as well as several different cross linker elements. The alkoxysilyl functionality can be distributed among these in any fashion as long as present somewhere in the polymer molecule.
Representative examples of alkoxysilyl functionality include groups such as CH2CH2Si(OR5)3, where R5 is methyl, ethyl, isopropyl, phenyl, benzyl or combinations of these.
For simplicity, throughout this disclosure and claims that follow, the term siloxane should be understood in its broad sense so as to include organo and other substituted siloxanes, polysiloxanes, and organo and other substituted polysiloxanes. This is of course understood to be distinct from a hydrocarbon. Reference to a combination of a siloxane and a hydrocarbon, should be taken to mean a hydrocarbon bridging two or more siloxanes or a siloxane bridging two or more hydrocarbons or something made up of two or more of these; such combination could be termed a siloxane of course, but not a hydrocarbon.
It should be understood that throughout this disclosure and the claims that follow that ranges should be interpreted as specifically including and disclosing all subranges and individual values subsumed. For example, a range of 1 to 10 would include and disclose a range of 2-5 and a range of 6-8, as well as 1.72, 7.76 and 9.9, among other subranges and individual vales in the overall range. Of course, this understanding would apply correspondingly to other types of ranges, such as xe2x80x9cC1 to C5 hydrocarbonsxe2x80x9d and xe2x80x9ca value of at least 80 percentxe2x80x9d.
In this disclosure and the claims that follow, it should be understood that a diluent may be a single compound or a mixture of compounds. Suitable examples include silicones such as siloxanes, both linear and cyclic (other than the corresponding cross-linked siloxane chosen for (A)), organic oils, organic solvents and mixtures of these. Some more specific examples of diluents may be found in U.S. Pat. No. 6,200,581, which is hereby incorporated by reference for this purpose. Non-reactive or relatively non-reactive diluents are preferred. For purposes here, non-reactive is used in reference to the associated cross-linking reaction and used relative to the (other) reactants therein. A relatively non-reactive diluent would be less than one tenth as reactive with the other reactants as the others are with each other in the associated cross-linking reaction.
As has previously been mentioned, alkoxysilyl functionality acts to increase durability (substantivity) in silicone based materials containing it, but there are aesthetic issues with the prior art materials. Surprisingly, in the compositions according to the present invention, durability rapidly reaches a suitable range for most personal care applications with increasing alkoxysilyl content without the negative effect on aesthetics of the prior art materials. The compositions according to the present invention are also good film formers with excellent aesthetics and have good bonding characteristics further enhancing their desirability in personal care applications. Given the wide variety of diluents that may be employed in making these compositions, compatibility is rarely ever an issue.
One embodiment of the explicitly defined compositions of the present invention that is of great interest is the material wherein:
(A) is a cross-linked alkoxysilyl functional siloxane of average formula: 
where,
R1 is a monovalent hydrocarbon group (preferably one having 1 to 30 carbons or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl, or combinations thereof with a very preferred choice being methyl);
R2 is xe2x80x94(CH2)dSiR4n(OR5)3-n;
R3 is xe2x80x94E1xe2x80x94Yxe2x80x94E2xe2x80x94R9 or a siloxane containing (somewhere in its structure as pendant, internal, terminal or otherwise) xe2x80x94E1xe2x80x94Yxe2x80x94E2xe2x80x94R9 with E1 in this last mentioned siloxane bonded to silicon as well as to Y,
R4 and R5 are independently monovalent hydrocarbon groups (preferably one having 1 to 30 carbons or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl, or combinations thereof, with very preferred choices for R5 including methyl, ethyl, isopropyl, phenyl or benzyl);
E1 and E2 are independently xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94;
Y is a divalent group that is a hydrocarbon (especially one having 1 to 30 carbons), a siloxane or some combination of these with one preferred Y being, 
where R10 is a monovalent hydrocarbon group (especially methyl) and p is 0 to 20,000 (especially 0 to 500);
R9 is 
(which can be thought of as the xe2x80x9cother sidexe2x80x9d of the cross link);
a is 0-100,000,000;
b is 1-50,000,000;
c is 1-10,000,000;
4 less than =cc less than =2c+2 (here and throughout cc represents a single value, not a product of c and c);
d is 2-12;
n is 0-2.
In reference to polymer formulae in this disclosure and the claims that follow, xe2x80x9caveragexe2x80x9d should be understood to be a number or molar average, unless otherwise indicated. Also in this disclosure and the claims that follow, it should be understood that that formulae given for polymers (such as the one for the cross linked siloxane given just above) should be regarded as only semi-structural such that the subscripts for various subunits indicate merely the number present in the molecule as opposed to the particular position shown. Further, no stereospecificity is intended by what is shown in such formulae.
A very suitable diluent (B) for this last embodiment is a siloxane other than that chosen for (A) or a mixture of siloxanes not containing that chosen for (A).
One preferred weight ratio range for (A):(B) for this embodiment is 1:100 to 10:1. This ratio is also generally applicable to other compositions of the present invention.
Another embodiment of the explicitly defined compositions of the present invention that is of great interest is the material wherein:
(A) is a cross-linked alkoxysilyl functional siloxane of average formula: 
where,
R11 is a monovalent hydrocarbon group (preferably having 1 to 40 or 1 to 20 carbons);
R42 is a monovalent hydrocarbon group (preferably having 1 to 40 or 1 to 20 carbons) or xe2x80x94(CH2)dSiR4n(OR5)3-n, with the proviso that R42 is at least in part xe2x80x94(CH2) dSiR4n(OR5)3-n;
R13 is xe2x80x94E1xe2x80x94R16xe2x80x94Yxe2x80x94R17xe2x80x94E2xe2x80x94R19, or a siloxane containing xe2x80x94E1xe2x80x94R16xe2x80x94Yxe2x80x94R17xe2x80x94E2xe2x80x94R19 with E1 in this last mentioned siloxane bonded to silicon and R16;
Q is on average at least 80 mole percent (SiO2) with the balance made up of one or more other types of siloxane units;
R4 and R5 are independently monovalent hydrocarbon groups (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof with R5 especially methyl, ethyl, isopropyl, phenyl or benzyl);
E1 and E2 are independently xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94;
R16 and R17 are independently divalent hydrocarbon groups (especially having 1 to 8 carbons) or nullities;
Y is a divalent group that is a hydrocarbon, a siloxane or a combination of these, with one preference being: 
where, R20 is a monovalent hydrocarbon group having from 1 to 40 carbons and v is 0 to 20,000 (especially 100 to 5,000 or 500 to 5,000);
R19 is 
(which can be thought of as the xe2x80x9cother sidexe2x80x9d of the cross link);
j is 1 to 100;
q is 1 to 500,000;
r is 1 to 1,000,000;
t is 1 to 100,000;
d is 2 to 12; and
n is 0 to 2, with the proviso that
q+t:r is 0.5 to 4.0 (here and throughout qj, rj and tj represent products of q and j, r and j, and t and j, respectively).
As is indicated here for R42, and should be taken as the case for other R and similarly designated groups throughout this disclosure and the claims that follow, variation is possible for a particular R or similarly designated group even within the same molecule. Of course, variation is limited to within the overall definition of the group. For example, if R100 is defined as a monovalent hydrocarbon group, then R100 might represent methyl groups in some and ethyl groups at other of the various positions it shows up in a particular molecule.
It should be understood that in this disclosure and the claims that follow that xe2x80x9csiloxane unitsxe2x80x9d refers to one of the silicon based building blocks found in siloxanes and polysiloxanes. These are commonly referred to in the art as xe2x80x9cMxe2x80x9d (xe2x89xa1SiO0.5), xe2x80x9cDxe2x80x9d (xe2x95x90SiO), xe2x80x9cTxe2x80x9d (xe2x80x94SiO1.5) and xe2x80x9cQxe2x80x9d (SiO2) units, as well as functionalized and/or substituted versions of these. One particular xe2x80x9cTxe2x80x9d type siloxane unit of interest in the immediately preceding embodiment of the compositions of the present invention is xe2x80x9cTxe2x80x94OHxe2x80x9d (HOxe2x80x94SiO1.5).
In the context of a divalent R or similarly designated divalent group, it should be understood that xe2x80x9cnullityxe2x80x9d means xe2x80x9cnothing therexe2x80x9d. For example, in xe2x80x94Xxe2x80x94Yxe2x80x94Zxe2x80x94, if xe2x80x94Yxe2x80x94 is a nullity, then xe2x80x94Xxe2x80x94Yxe2x80x94Zxe2x80x94 is the same as xe2x80x94Xxe2x80x94Zxe2x80x94.
The cross-linked component of the compositions of the present invention is often made up of enormous polymer molecules. Sometimes it may be convenient to describe this component and the overall composition in terms of subunits. This concept is utilized in describing yet another embodiment of the explicitly defined compositions of the present invention wherein:
(A) is a cross-linked alkoxysilyl functional siloxane comprising subunits of formula 
where,
R1 is a monovalent hydrocarbon group (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof);
R2 is xe2x80x94(CH2)dSiR4n(OR5)3-n;
R3 is xe2x80x94E1xe2x80x94Yxe2x80x94E2xe2x80x94R9 or a siloxane containing (somewhere in its structure as pendant, internal, terminal or otherwise) xe2x80x94E1xe2x80x94Yxe2x80x94E2xe2x80x94R9 with E1 in this last mentioned siloxane bonded to silicon as well as to Y,
R4 and R5 are independently monovalent hydrocarbon groups (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof with R5 especially methyl, ethyl, isopropyl, phenyl or benzyl);
E1 and E2 are independently xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94;
Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these;
R9 is 
(which may be thought of as the xe2x80x9cother sidexe2x80x9d of the cross-link);
a is 0-1,000;
b is 1-500;
c is 1-100;
4 less than =cc less than =2c+2;
d is 2-12; and
n is 0-2.
As in the polymer formulae of this disclosure and the claims that follow, those given for polymer subunits as here should be regarded as only semi-structural such that the subscripts for various units indicate merely the number present in the subunit as opposed to the particular position shown. Further, no stereospecificity is intended by what is shown in such formulae.
Another embodiment of the explicitly defined compositions of the present invention also with component (A) expressed in terms of subunits is one wherein:
(A) is a cross-linked alkoxysilyl functional siloxane comprising subunits of formula: 
where,
R11 is a monovalent hydrocarbon group (preferably having 1 to 40 or 1 to 20 carbons);
R42 is a monovalent hydrocarbon group (preferably having 1 to 40 or 1 to 20 carbons) or xe2x80x94(CH2)dSiR4n(OR5)3-n, with the proviso that R42 is at least in part xe2x80x94(CH2) dSiR4n(OR5)3-n;
R13 is xe2x80x94E1xe2x80x94R16xe2x80x94Yxe2x80x94R17xe2x80x94E2xe2x80x94R19, or a siloxane containing xe2x80x94E1xe2x80x94R16xe2x80x94Yxe2x80x94R17xe2x80x94E2xe2x80x94R19 with E1 in this last mentioned siloxane bonded to silicon and R16;
Q is on average at least 80 mole percent (SiO2) with the balance made up of one or more other types of siloxane units (as defined previously, including xe2x80x9cTxe2x80x94OHxe2x80x9d);
R4 and R5 are independently monovalent hydrocarbon groups (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof with R5 especially methyl, ethyl, isopropyl, phenyl or benzyl);
E1 and E2 are independently xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94;
R16 and R17 are independently divalent hydrocarbon groups or nullities;
Y is a divalent group that is a hydrocarbon, a siloxane or a combination of these
R19 is 
(which can be thought of as the xe2x80x9cother sidexe2x80x9d of the cross-link);
j is 1 to 100;
q is 1 to 500;
r is 1 to 1000;
t is 1 to 100;
d is 2 to 12; and
n is 0 to 2, with the proviso that
q+t:r is 0.5 to 4.0.
The present invention also relates to methods of making the compositions previously described and compositions related to them as described below that are also part of the invention. Thus, the methods of the present invention are for making thermodynamically stable materials, the methods comprising cross-linking, in the presence of a hydrosilylation catalyst:
(1) an xe2x89xa1SiH functional siloxane and
(2) an alpha, omega diene, diyne or ene-yne (as defined herein below), with the provisos
that at least one of (1) and (2) (very often (1)) has alkoxysilyl functionality,
xe2x80x94Xxe2x80x94SiR4n(OR5)3-n,
where,
X is a divalent group that is a hydrocarbon (preferably having 2 to 12 carbons), a siloxane or some combination of these,
R4 and R5 are independently monovalent hydrocarbon groups and n is 0 to 2,
that (1) and (2) are dispersed in a diluent (which may be a single compound or mixture as previously discussed), and
that the weight ratio of (1)+(2)+ the product of the cross-linking of (1) and (2):diluent is 1:100 to 10:1.
Any hydrosilylation catalyst, of which many are well known in the art, may be utilized, such as those based on noble metals like platinum, notably Karstedt""s catalyst. Karstedt""s catalyst, a platinum divinyl tetramethyl disiloxane based composition, is described extensively in the art such as in U.S. Pat. No. 5,654,362. Homogeneous, heterogeneous or mixtures of homogeneous and heterogeneous form catalysts may be employed.
It may be advantageous in some instances to control reaction using a catalyst quencher. Quenching of this type is presented in U.S. Pat. No. 5,929,164. It is not essential that a quencher be used in the methods of the present invention, but one may be employed if desired.
In this disclosure and the claims that follow, especially in the context of the methods of the present invention, xe2x89xa1SiH functionality should be understood in its broad sense. That is it may be pendant, internal, terminal or otherwise or some combination of these. It may be of note (and is shown in the examples) that alkoxysilyl functionality is often introduced in a hydrosilylation step prior to the cross-linking step shown above with only a portion of the available xe2x89xa1SiH consumed in this prior step.
Especially in the context of the methods of the present invention, but also generally in this disclosure and the claims that follow, xe2x80x9calpha, omega diene, diyne or ene-ynexe2x80x9d should be understood to refer to compounds wherein there is at least a pair of terminal aliphatic unsaturated groups with some separation. Structurally, this would (in the xe2x80x9calpha, omega diynexe2x80x9d case) look something like HCxe2x89xa1Cxe2x80x94Lxe2x80x94Cxe2x89xa1CH, where L could be for example hydrocarbon, siloxane or some combination of these. The unsaturation could be at an end or pendant if part of a polymer or resin molecule.
An embodiment of the methods of the present invention of great interest is one where,
(1) is an alkoxysilyl functional siloxane of average formula: 
where,
R1 is a monovalent hydrocarbon group (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof);
R2 is xe2x80x94(CH2)dSiR4n(OR5)3-n;
R4 and R5 are independently monovalent hydrocarbon groups (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof with R5 especially methyl, ethyl, isopropyl, phenyl or benzyl);
a is 0-1,000;
b is 1-500;
c is 1-100;
2 less than =cc less than =2c+2;
d is 2-12; and
n is 0-2;
(2) is E3xe2x80x94Yxe2x80x94E4 or a siloxane containing (somewhere in its structure as pendant, internal, terminal or otherwise) E3xe2x80x94Yxe2x80x94E4, where
E3 and E4 are independently CH2xe2x95x90CHxe2x80x94 or CHxe2x89xa1Cxe2x80x94; and
Y is a multivalent group (divalent or higher valency) that is a hydrocarbon, a siloxane or some combination of these.
Another embodiment of the methods of the present invention of great interest is one where,
(1) is on average,
[(CH3)3SiO0.5]i[(CH3)2HSiO]u[(CH3)2SiO]c[(CH3) HSiO]d[(CH3)R2SiO]k[(CH3)2R2SiO0.5]m;
R2 is xe2x80x94(CH2)pSiR4n(OR5)3-n;
R4 and R5 are independently monovalent hydrocarbon groups, (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof with R5 especially methyl, ethyl, isopropyl, phenyl or benzyl);
i is 0 to 2;
u is 0 to 2;
i+u+m=2;
c is 0 to 20,000 (preferably 100 to 5000 or 500 to 5000);
d is 0 to 2000 (preferably 0 to 200);
u+d greater than =2;
k is 0 to 2000 (preferably 0 to 500);
m is 0 to 2;
k+m greater than =1;
p is 2 to 12;
n is 0 to 2; and
(2) is on average
[(CH2xe2x95x90CH)(CH3)2SiO0.5]e[(CH3)3SiO0.5]f[(CH3)2SiO]g[(CH2xe2x95x90CH)(CH3)SiO]h;
e is 0 to 2;
f is 0 to 2;
e+f=2;
g is 0 to 20,000 (preferably 0 to 500);
h is 0 to 1000 (preferably 0 to 50);
e+h greater than =2
Still another embodiment of the methods of the present invention of great interest is one where,
(1) is on average 
where,
R11 is a monovalent hydrocarbon group (preferably having 1 to 40 or 1 to 20 carbons);
R42 is a monovalent hydrocarbon group (preferably having 1 to 40 or 1 to 20 carbons) or xe2x80x94(CH2)dSiR4n(OR5)3-n, with the proviso that R42 is at least in part xe2x80x94(CH2) dSiR4n(OR5)3-n;
Q is on average at least 80 mole percent (SiO2) with the balance made up of one or more other types of siloxane units (as defined previously including xe2x80x9cTxe2x80x94OHxe2x80x9d);
R4 and R5 are independently monovalent hydrocarbon groups (preferably having 1 to 30 or 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl or combinations thereof with R5 especially methyl, ethyl, isopropyl, phenyl or benzyl);
j is 1 to 100;
q is 1 to 500;
r is 1 to 1000;
t is 1 to 100;
d is 2 to 12;
n is 0 to 2;
q+t:r is 0.5 to 4; and
(2) is on average 
where x is 0 to 20,000 (preferably 100 to 20,000 or 100 to 5000);
y is 0 to 2000,
z is 0 to 2,
2 less than =z+y less than =2000,
R21 is a monovalent, terminally aliphatic unsaturated hydrocarbon having from two to twelve carbons, and
R22 is a monovalent hydrocarbon having one to forty carbons.
Yet another embodiment of the methods of the present invention of great interest is one where,
(1) is an xe2x89xa1Sixe2x80x94H functional polyorganosiloxane and
(2) is a polyorganosiloxane resin having alpha-omega diene, diyne or ene-yne (as defined previously) functionality.
An important refinement of this last embodiment is one where at least 80 mole percent of subunits in the polyorganosiloxane resin of (2) are (SiO2) and ((Ri)3SiO0.5), where Ri is a monovalent hydrocarbon group, the ratio in (2) of siloxane units other than SiO2 to SiO2 units there is 0.5 to 4.0, and X in the alkoxysilyl functionality is a hydrocarbon.
It is sometimes convenient to express a composition (implicitly) in terms of a method to make it. This invention includes compositions that are the product of (made by, prepared by, etc.) any of the methods of the present invention.
The compositions of the present invention are often clear and nearly solid materials. These may be diluted with a suitable diluent to form pastes, gels or fluids as required.
The invention also includes compositions, such as personal care products, made from any of the compositions of the present invention previously described herein. This would include hair, skin and underarm care products. Some more specific examples would be conditioners, moisturizers, body washes, cosmetic foundations, blushes, lipsticks, eye liners, mascaras, eye shadows, antiperspirants and deodorants. Other examples of products that can be made from the compositions of the present invention are the same as can be made from the materials disclosed in U.S. Pat. No. 6,200,581, which is hereby incorporated by reference for these examples.
In this disclosure and the claims that follow, it should be understood that in the context of a chemical formula that Me stands for methyl. Further, compositions expressed in percent should be taken as being in weight percent, unless otherwise indicated.
Titles in the examples that follow are merely descriptive and should not be viewed as limiting in any way.